Nonreductive deiodination of ortho-iodo-hydroxylated arenes using tertiary amines

A convenient and nonreductive deiodination is reported for the ortho-iodo-hydroxylated arenes including derivatives of quinolinol, phenol, and naphthol. Tertiary amines pyridine, triethylamine, and N-methylmorpholine in the presence of water initiated deiodination of ortho-iodo-hydroxylated arenes without affecting para-iodine and other reduction-susceptible groups. This reported method also works efficiently for polyiodinated systems. Simplicity, short reaction times, and absence of reducing catalyst are features of this method.     

Experimental estimation of the interaction parameter eO for ZnN

The use of dislocation measurements in Zinc single crystals reveals the presence of a yield point or flow stress corresponding to a Stages I–II (elastic to elastic-plastic) transition. This is commonly attributed to the presence of interstitials such as N. The mathematical models of Seeger and Dorn and Rajnak are used to evaluate certain microstructural parameters. These correlate favourably with experimental values. The excess work done over that to overcome the Peierls and frictional forces is then calculated per pair of pinning interstitials and equated to the energy of formation of a molecule of Zn₃N₂ which is believed to form. The results show that this assumption does lead to the stochiometry Zn₃N₂, thus verifying mathematical parameters from different equations using work-energy concepts. Use of the mechanical equivalent J also seems to indicate a favourable correlation for the stochiometry of Zn₃N₂, and for e_O as calculated calorimetrically.     

Imaging electron trajectories in a laser-wakefield cavity using betatron X-ray radiation

We demonstrate that betatron x-ray radiation accurately provides direct imaging of electrons trajectories accelerated in laser wakefields. Experimental far field x-ray beam profiles reveal that electrons can follow similar transverse trajectories with typical excursions of 1.5 microm+/-0.5 microm in the plane of laser polarization and 0.7 microm+/-0.2 microm in the plane perpendicular.     

Analysis and parametric optimization of 1H off-resonance relaxation NMR experiments designed to map polypeptide self-recognition and other noncovalent interactions

The measurement of 1H off-resonance nonselective relaxation rates (R(theta,ns)) has been recently proposed as an effective method to probe peptide self-recognition, opening new perspectives in the understanding of the prefibrillization oligomerization processes in amylodogenesis. However, a full analysis and parametric optimization of the NMR experiments designed to measure R(theta,ns) relaxation rates is still missing. Here we analyze the dependence of the R(theta,ns) rates upon three critical parameters: the tilt angle of the effective field during the spin lock, the static magnetic field, and finally the repetition delay. Our analysis reveals that the tilt angle theta = 35.5 degrees not only minimizes spin-diffusion, but also avoids experimental artifacts such as J-transfer and poor adiabaticity. In addition, we found that when the dominant relaxation mechanism is caused by uncorrelated pairwise 1H dipole-1H dipole interactions the R(35.5 degrees,ns) rate is not significantly affected by static field variations, suggesting a wide applicability of the 1H off-resonance nonselective relaxation experiment. Finally, we show that the self-recognition maps based on the comparative analysis of the R(35.5 degrees,ns) rates can tolerate decreases in the interscan delays without significantly compromising the identification of critical self-association loci. These considerations not only provide a better understanding of the 1H off-resonance nonselective relaxation, but they also serve as guidelines for the optimal setup of this experiment.     

Determination of carbon nanotube density by gradient sedimentation

Density gradient centrifugation is a high-resolution technique for the separation and characterization of large molecules and stable complexes. We have analyzed various nanotube structures by preparative centrifugation in sodium metatungstate-water solutions. Bundled, isolated and acid-treated single-walled nanotubes (SWNTs) and multiwall nanotubes (MWNTs) formed sharp bands at well-defined densities. The structure of the material in each band was confirmed by transmission electron microscopy and Raman spectroscopy. Our data suggest respective densities of 1.87, 2.13, 1.74, and 2.1 g/cm(3) for bundled, isolated, and acid-treated SWNTs and MWNTs. These measured results compare well with their calculated densities.     

Topological Majorana and Dirac zero modes in superconducting vortex cores

We provide an argument based on flux insertion to show that certain superconductors with a nontrivial topological invariant have protected zero modes in their vortex cores. This argument has the flavor of a two-dimensional index theorem and applies to disordered systems as well. It also provides a new way of understanding the zero modes in the vortex cores of a spinless px+ipy superconductor. Applying this approach to superconductors with and without time-reversal and spin-rotational symmetry, we predict the necessary and sufficient conditions for protected zero modes to exist in their vortices.     

Multimodal nonlinear optical polarizing microscopy of long-range molecular order in liquid crystals

We demonstrate orientation-sensitive multimodal nonlinear optical polarizing microscopy capable of probing orientational, polar, and biaxial features of mesomorphic ordering in soft matter. This technique achieves simultaneous imaging in broadband coherent anti-Stokes Raman scattering, multiphoton excitation fluorescence, and multiharmonic generation polarizing microscopy modes and is based on the use of a single femtosecond laser and a photonic crystal fiber as sources of the probing light. We show the viability of this technique for mapping of three-dimensional patterns of molecular orientations and show that images obtained in different microscopy modes are consistent with each other.     

Direct probing of sorbent-solvent interactions for amylose tris(3,5-dimethylphenylcarbamate) using infrared spectroscopy, X-ray diffraction, solid-state NMR, and DFT modeling

The sorbent-solvent interactions for amylose tris(3, 5-dimethylphenylcarbamate) (ADMPC) with five commonly used solvents, hexane, methanol, ethanol, 2-propanol (IPA), and acetonitrile (ACN), are studied using attenuated total reflection infrared spectroscopy (ATR-IR) of thin sorbent films, X-ray diffraction (XRD) of thin films, (13)C cross polarization/magic angle spinning (CP/MAS) and MAS solid state NMR of polymer-coated silica beads (commercially termed "Chiralpak AD"), and DFT modeling. The ADMPC-polymer-coated silica beads are used commercially for analytical and preparative scale separations of chiral enantiomers. The polymer forms helical rods with intra- and inter-rod hydrogen bonds (H-bonds). There are various nm-sized cavities formed between the polymer side-chains and rods. The changes in the H-bonding states of the C=O and NH groups of the polymer upon absorption of each of the five solvents at 25 degrees C are determined with ATR-IR. The IR wavenumbers, the H-bonding interaction energies, and the H-bonding distances of the polymer side-chains with each of the solvent molecules are predicted using the DFT/B3LYP/6-311+g(d,p) level of theory. The changes in the polymer crystallinity upon absorption of each solvent are characterized with XRD. The changes in the polymer crystallinity and the H-bonding states of C=O groups are also probed with (13)C CP/MAS solid-state NMR. The changes in the polymer side-chain mobility are detected using (13)C MAS solid-state NMR. The H-bonding states of the polymer change upon absorption of each polar solvent and usually result in an increase in the polymer crystallinity and the side-chain mobility. The polymer rods are reorganized upon solvent absorption, and the distance between the rods increases with the increase in the solvent molecular size. These results have implications for understanding the role of the solvent in modifying the structure and behavior of the polymer sorbents.     

On the structural properties of small-world networks with range-limited shortcut links

We explore a new variant of Small-World Networks (SWNs), in which an additional parameter (r$r$) sets the length scale over which shortcuts are uniformly distributed. When r=0$r=0$ we have an ordered network, whereas r=1$r=1$ corresponds to the original Watts–Strogatz SWN model. These limited range SWNs have a similar degree distribution and scaling properties as the original SWN model. We observe the small-world phenomenon for r?1$r?1$, indicating that global shortcuts are not necessary for the small-world effect. For limited range SWNs, the average path length changes nonmonotonically with system size, whereas for the original SWN model it increases monotonically. We propose an expression for the average path length for limited range SWNs based on numerical simulations and analytical approximations.